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Chapter 2

Dilute Acid Hydrolysis of Agro-Residues


for the Depolymerization
of Hemicellulose: State-of-the-Art
Anuj K. Chandel, Felipe A. F. Antunes, Priscila Vaz de Arruda,
Thais S. S. Milessi, Silvio S. da Silva and Maria das Graas de
Almeida Felipe

Abstract Geo-political, long-term economic and sustainable concerns are


promoting researchers and entrepreneurs to harness the potential of lignocellulosic
feedstock (LCF) into industrially significant products. Agro-residues (sugarcane
bagasse, wheat straw, rice straw, corn stover, etc.) constitute the principal fraction
of LCF and are available in large amounts globally. The judicious exploration of
agro-residues into important products such as D-xylitol, an artificial sweetener, may
provide a strong platform for its sustainable supply to the medical and non-medical
applications-based sectors. Pretreatment of agro-residues by dilute acid hydrolysis
is an inevitable process for the depolymerisation of hemicellulosic fraction into
xylose and other sugars. Dilute acid catalyses hemicellulose fractionation at high
temperature within short reaction times. Significant developments have been made
in the past towards the chemical hydrolysis of agro-residues, particularly for the
hemicellulose breakdown. Critical parameters such as acid load, temperature,
residence time and solid-to-liquid ratio play pivotal roles in the kinetics of dilute
acid hydrolysis of agro-residues. Furthermore, reactor configurations such as
counter-current, plug-flow, percolation and shrinking-bed have been designed in
order to maximize the sugars recovery with minimum inhibitors generation. This
chapter reviews the process parameters, kinetics, methods and reactor engineering
for the dilute acid catalysed processes employed for agro-residues.

Keywords Agro-residues Dilute acid hydrolysis Hemicellulose depolymerization Pretreatment Reaction kinetics Reactor design

A. K. Chandel (&)  F. A. F. Antunes  P. V. de Arruda 


Thais S. S. Milessi  S. S. da Silva  M. das G. de Almeida Felipe (&)
Department of Biotechnology, Engineering School of Lorena, University of So Paulo,
Lorena- 12.602.810 So Paulo, Brazil
e-mail: anuj.kumar.chandel@gmail.com; kumar10@debiq.eel.usp.br
M. das G. de Almeida Felipe
e-mail: mgafelipe@debiq.eel.usp.br

S. S. da Silva and A. K. Chandel (eds.), D-Xylitol,


DOI: 10.1007/978-3-642-31887-0_2, Springer-Verlag Berlin Heidelberg 2012

39

40

A. K. Chandel et al.

2.1 Introduction
The low cost and renewable nature of agro-residues such as sugarcane bagasse,
wheat straw, rice straw, corn stover, etc. represent the ideal feedstock for their
conversion into value-added products by biotechnological routes (Mantanis et al.
2000; Mussatto and Teixeira 2010). These agro-residues, like other lignocellulosic
materials, are constituted primarily of lignin, hemicellulose(s) and cellulose. The
carbohydrate fraction (hemicellulose and cellulose) can be depolymerised into
sugars which act as a primary carbon source for the microbial biocatalysts for the
production of xylitol, ethanol, organic acids, industrial enzymes, etc. (Carvalheiro
et al. 2008; Mussatto and Teixeira 2010; Chandel et al. 2011a). Figure 2.1 demonstrates the process configuration for dilute acid hydrolysis of various agroresidues into monomeric constituents and subsequently their conversion into
value-added products by microbial fermentation. Due to the large variations of the
chemical compositions of agro-residues, especially polysaccharides and lignin, it
is important to choose an appropriate method of biomass fractionation for their
effective biotechnological utilization (Howard et al. 2003). In this context, the
complex cellular structure of the agro-residues must be fractionated into C6 or C5
sugars with minimum side (or by)-products (Mosier et al. 2005). Thus the procedure applied will be a hydrolysis and/or a pretreatment, depending on the purpose of the released sugars.
During the acid hydrolysis of the hemicellulose fraction of plant cell wall,
sugars are liberated in addition to some undesired compounds. The recovered solid
residue, so-called cellulignin, is readily available for the subsequent cellulasesmediated enzymatic hydrolysis into glucose. Thus the pretreatment step involving
dilute acid facilitates the enzymes accessibility to the cellulose for maximizing
sugars recovery (Chandel et al. 2011b). Dilute acid hydrolysis is a simple and fast
method to obtain hemicellulosic hydrolysates. These hydrolysates mainly contain
xylose (80 % of the sugar content in hemicellulosic fraction), arabinose, glucose,
galactose and mannose in conjunction with cell wall-derived inhibitors such as
furans, phenolics, weak acids and others (Canilha et al. 2006, 2008; Chandel et al.
2007a).
During dilute acid hydrolysis of agro-residues, parameters such as temperature,
time, acid concentration and solid-to-liquid ratio play critical roles in obtaining
optimum sugar recovery and minimum generation of inhibitors (Taherzadeh and
Karimi 2007). The establishment of these parameters is of fundamental importance
to define optimal conditions of hydrolysis to ensure the success of the process, in
view of concerns taken into account since the hydrolyzate will be used as
fermentation medium (Grio et al. 2010). Thus, the knowledge about the cell wall
chemical composition of agro-residues is very important in order to identify the
raw materials with higher content of hemicellulose and bioprocesses using pentose
sugars as substrates for the production of several chemical commodities (Saha
2003). The choice of the optimal hydrolysis conditions is very important for
maximum yield of sugars and minimal formation of toxic compounds for the

2 Dilute Acid Hydrolysis of Agro-Residues

41

Fig. 2.1 Process configuration summarizing the dilute acid hydrolysis of various agro-residues
into monomeric constituents and their conversion into value-added products

utmost production of compounds after fermentation reaction. This should be a


low-cost process to ensure the sustainability of this technology and successful
agro-residual feedstock management (Mantanis et al. 2000; Mussatto and Teixeira
2010; Chandel et al. 2010a). In this context, designing of reactors or changes in
their configuration is an important consideration for the maximum de-polimerization of hemicellulose during dilute acid hydrolysis (Mosier et al. 2005;
Thaerzadeh and Karimi 2007; Lenihan et al. 2011). The emergence of plug-flow
reactors (PFR), counter-current reactors, percolation reactors and shrinking bed
counter current reactors have shown promising results for dilute acid mediated
hydrolysis of agro-residues (Lee et al. 1999; Taherzadeh and Karimi 2007;
Lenihan et al. 2011). Among all these process configurations, counter-current
reactors have shown better results for the maximum hemicellulosics breakdown
with fast reaction rates consequently producing low concentration of cell-wall
derived inhibitors (Lee et al. 1999). However, a considerable amount of work is
still required to establish a robust and reproducible technology for the maximum
hemicellulose de-polimerization at industrial scale.
This chapter discusses the chemical nature and influential parameters of dilute
acid hydrolysis of agro-residues, hydrolysis kinetics with sugar recovery, and the
improvements in reactor configuration for maximum hemicelluloses de-polimerization into their monomeric constituents.

42

A. K. Chandel et al.

2.2 Cell Wall Chemistry of Various Agro-Residues


The cell wall consists of three main components: cellulose microfibrils (with
characteristic distributions and organization), hemicellulose and lignin. Also,
smaller amounts of pectin, protein, extractives and ash are found. The structure of
these materials is very complex, and native biomass is generally resistant to
chemical/enzymatic hydrolysis (Saha 2003).
The lignocellulosic biomass chemical composition differs with the source of
plant species (Table 2.1). Cellulose is the main constitute(s) of bagasses and
straws. The highest content of this fraction was found for sugarcane bagasse, an
average of 42.845.0 %. Hemicellulose is the second major compound of these
biomass sources, usually between 22 and 35 % of dry mass. Celluloses and most
of the hemicelluloses are structural carbohydrates as they form the bulk of the
plant cells supporting structure (Ek et al. 2009). Coffee husk showed the highest
hemicellulosic content (36.7 %) of the materials available, while sunflower stalks
showed the lowest (20.2 %). In general, straws showed higher lignin content than
others materials. For instance, sugarcane leaves straw showed high lignin content
(2632 %). According to Ek et al. (2009), the lignin contents in non-woody plants
are, however, much lower (120 %) than in woody plant tissues. There is also a
variation in cell wall composition between individual biomass sources of the same
plant species, depending on the age of plant, genetic factors and growth conditions,
e.g. climatologic and geographic factors (Ek et al. 2009). Cellulose is the most
common polysaccharides in nature and consists of repeating units of cellobiose. It
is a glucan polymer of D-glucopyranose units, which are linked together by
b-(1 ? 4)-glucosidic bonds (Rowell et al. 2005). The number of glucose units in
one wood cellulose molecule (i.e. the degree of polymerization) is at least
9,00010,000 and possibly as high as 15,000 (Rowell et al. 2005). In this case,
cellulose molecules aggregate with each other due to hydrogen bonding and form
microfibrils, which are the building blocks of fibrils, and in turn build the cellulose
fiber (Sjstrm 1993).
In general, the hemicellulose fraction is a polymer that is composed of several
different sugars like D-glucose, D-mannose, D-galactose, D-xylose, L-arabinose,
L-rhamnose and is sometimes referred to by the sugars they contain, for example,
galactoglucomannan, arabinoglucoronoxylan, arabinogalactan, glucuronoxylan,
glucomannan, etc. The hemicellulose also contains acetyl and methyl substitute
groups (Rowell et al. 2005). The degree of polymerization of hemicellulose is
lower than cellulose, achieving an average of about 100200 and the molecules
can be highly branched (Rowell et al. 2005). Due to the combination of several
sugars and for presenting majority part of amorphous structure, the hemicellulose
is more soluble in water and easily degraded than cellulose. In the lignocellulosic
materials the cellulose and lignin are intimately linked, because hemicellulose acts
as glue between those fractions (Fengel and Wegener 1984).
Next to cellulose, lignin is the most abundant and important polymeric organic
substance in the plant world. Lignin increases the mechanical strength properties

2 Dilute Acid Hydrolysis of Agro-Residues

43

Table 2.1 Cell wall composition of various agro-residues (% of dry material)


Lignocellulosic source Components
References
Cellulose Hemicellulose

Lignin Extractives Ash

40.4
42.8

35.5
25.9

3.9
22.1

na
6.1

43.1
43.8
45.0

25.2
27.0
26.0

22.9
22.6
20.0

4.3
3.9
na

Barley spent 27.6


16.8
Brewery0 s
spent
21.2
Coffee spent 8.6

32.5
28.4

13.4
27.8

12.9
5.8

30.4
36.7

22.2
na

na
na

Oat

29.3

28.4

22.2

na

Rice

21.5

23.1

14.6

na

Corn
Rice

34.4
43.4

29.0
22.9

17.2
17.2

na
na

Sorghum

35.1

24.0

25.4

na

Sugarcane

40.8
33.6

30.8
28.9

25.8
31.8

na
na

Wheat

33.0

33.0

20.0

na

Corn cobs
Sunflower
stalks

42.7
33.8

34.3
20.2

18.4
17.3

3.0
6.9

Bagasse Sorghum
Sugarcane

Grains

Husk

Straw

Others

0.2
1.4

Dogaris et al.(2009)
Silva et al. (2010a,
b, c)
2.8 Rocha et al. (2012)
2.0 Martn et al. (2011)
2.1 Boussarsar et al.
(2009)
3.4 Dehnavi, (2009)
4.6 Mussatto et al.
(2007)
1.1 Duarte et al. (2008)
1.6 Mussatto et al.
(2011)
4.5 Tamanini et al.
(2004)
na Megawati et al.
(2011)
na Bura et al. (2009)
11.4 Roberto et al.
(2003)
na Tllez-Luiz et al.
(2002)
2.6 Mouta et al. (2011)
5.7 Silva et al. (2010a,
b, c)
na Canilha et al.
(2006)
na Cheng et al. (2009)
9.6 Ruiz et al. (2008)

na not available

to such an extent that huge plants such as trees with heights to even more than
100 m can remain upright (Fengel and Wegener 1984). Lignins are complex
polymers consisting of phenyl propane units linked together by ether or carbon
carbon bonds (Brunow et al. 1999). Lignins can be classified in several ways, but
they are usually divided according to their structural elements (Sjstrm 1993). All
wood lignins consist mainly of three basic building blocks of guaiacyl, syringyl,
and p-hydroxyphenyl moieties, although other aromatic units also exist in many
different types of woods. There is a wide variation of structures within different
wood species. The lignin content of hardwoods is usually in the range of 1825 %,
whereas the lignin content of softwoods varies between 25 and 35 % (Rowell et al.
2005).

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A. K. Chandel et al.

2.3 Bioconversion of Xylose and Other Hemicellulosic Sugars


into Bioactive Products
Agro-industrial wastes/byproducts represent a large portion of biomass which does
not compete with food production (Doherty et al. 2011). Considering the large
amount of agro-industrial byproducts discarded, the development of a technological platform for the production of any value-added product has yet to be
established on a large scale (Felipe et al. 1997).
The conversion of the hemicellulosic fraction to fermentable sugars is essential
for its use in various biochemical processes (Chandel et al. 2010b; Grio et al.
2010). Due to the recalcitrant characteristic of agro-residues, a pretreatment step
can depolymerise the hemicellulosic fraction into fermentable sugars such as
xylose, glucose and arabinose (Mosier et al. 2005). These hemicellulosic-derived
sugar solutions are used for the production of commercially significant products.
A wide variety of pretreatment methods aiming at hemicellulose de-polimerization
such as dilute acid hydrolysis, steam explosion, and liquid hot water pretreatment
have been developed (Mosier et al. 2005). Among these methods, dilute acid
mediated hydrolysis has been found more effective towards complete hemicellulose hydrolysis in short reaction times (Taherzadeh and Karimi 2007). Acid
hydrolysis with dilute sulfuric acid under mild conditions has proven to be a
method that is reliable, easy to operate and low cost (Shatalov and Pereira 2012).
Table 2.2 summarizes the examples of various bioproducts of commercial
interest produced by microbial fermentation using the sugars derived from agroresidues.
The application of xylose in xylitol production has being widely studied.
Xylitol is a polyalcohol with great importance in food, pharmaceutical and dental
care industries because of its interesting properties, as its sweetness is metabolically independent of insulin and anticariogenic properties (Milessi et al. 2011).
Branco et al. (2008) obtained a conversion of xylose to xylitol (0.87 g/g) using the
yeast Candida guilliermondii in a bench reactor. Rodrigues et al. (2011) recently
evaluated xylitol production (0.61 g/g) from Pichia stipitis YS-30 using corn
stover acid hydrolysate. Hemicellulose hydrolysate from various agro-residues has
shown great potential in other added value products such as ethanol (Chandel et al.
2007a; Mouta et al. 2011), citric acid (Kirimura et al. 1999), lactic acid (Ou et al.
2011), single cell protein (SCP) (Anupama and Ravindra 2000), and 2,3-butanediol (Zhao et al. 2011). Recently, Rabelo et al. (2011) evaluated the potential of
hemicellulose-derived sugar solution for biogas production.
Looking at the potential of pentose sugars as fermentable feedstock for the
production of commercially valuable products, the importance of pentose sugars
recovery and subsequently their utilization in fermentation processes is highly
remarkable.

S:L solid:liquid ratio, n.d. not detected

De-oiled
3.5 % v/v H2SO4, 120 C, S:L = 1:10,
60 min
rice bran
Barley bran 3 % w/v H2SO4, 120 C, S:L = 1:10,
60 min

Rice straw

TRS, 38.50 0.45

1.5 % H2SO4, 130 C, 30 min, S: L = 1:10 Xylose, 17.2; Glucose, 4.3; Arabinose,
3.3
Xylose, 12.80 0.25; D-glucose,
Wheat straw 1.85 % (w/v) H2SO4, 90 C, 18 h, S:
L = 1:20
1.70 0.30; L -arabinose,
2.60 0.21
Xylose, 9.09; Glucose, 2.13; Arabinose,
Corn stover 2.13 % H2SO4, 180 min, 121 C, S:
L = 1:10
1.01
Sugarcane
2.5 % (v/v) HCl, 140 C, 30 min, S:
Total reducing sugars (TRS), 30.29
bagasse
L = 1:10
Xylose, 26.7; Arabinose, 12.8; Glucose,
Brewarys
Combined severity, 1.94 (3 % (w/w)
4.0
spent
H2SO4, 130 C, 15 min, S:L = 8 % w/
w)
grain
Total reducing sugars (TRS), 56.5
Sugarcane
130 C, 2.9 % H2SO4 w/v, S:L = 1:4,
30 min
leaves
straw
Xylose, 54.2; Glucose, 13.5; Arabinose,
Sorghum
2 % H2SO4, 122 C, 71 min
12
straw

Reference

n.d.

n.d.

Furfural, 0.2; acetic acid, 0.00

Acetic acid, 1.48; Furans, 0.56;


Phenolics, 0.08
Furans, 1.89; Phenolics, 2.75;
Acetic acid, 5.45
Acetic acid, 1.5; Formic acid, 0.23;
Furfural, 0.29; HMF, 0.02;
Total phenolics 0.91
Acetic acid, 3.19; Furfural, 0.56;
HMF, 0.15

SeplvedaHuerta et al.
(2006)
Chandel et al.
(2009)
Cruz et al.
(2000)

Mouta et al.
(2011)

Chandel et al.
(2007a)
Carvalheiro
et al. (2004)

Cao et al. (2009)

Acetate, 1.43; HMF, 0.15;


Baek and Kwon
Furfural, 0.25
(2007)
Furfural, 0.15 0.02; acetic acid, Nigam (2001)
2.70 0.33

Table 2.2 Dilute acid hydrolysis of various agro-residues for the production of hemicellulosic-derived products
AgroConditions for acid hydrolysis
Sugars (g/L)
Inhibitors (g/L)
residue

2 Dilute Acid Hydrolysis of Agro-Residues


45

46

A. K. Chandel et al.

2.4 Factors Influencing the Dilute Acid Hydrolysis


of Agro-Residues
The achievement of high levels of sugar after pretreatment is a crucial factor for
the commercial competitiveness of the use of lignocellulosic materials. Pretreatment in the form of dilute acid hydrolysis is one of the most important cost
contributing factors in overall bioconversion processing of agro-residues (Yang
and Wyman 2008; Chandel et al. 2010a). Furthermore, dilute acid hydrolysis
facilitates the enzymatic hydrolysis of the remaining cellulosic fraction into
glucose (Chandel et al. 2011b). Pretreatment of agro-residues with diluted acid has
been extensively studied and found to be an efficient method for recovery of
fermentable sugars (Laopainboon et al. 2010; Akpinar et al. 2009). Dilute acid
hydrolysis has the advantage over concentrated acid hydrolysis due to equipment
corrosion (Grio et al. 2010). However, this process has the disadvantage of
formation of cell wall-derived inhibitors such as furfural and 5-hydroxymethylfurfural (HMF), weak acids, phenolics and others evidencing the importance of the
optimization of the conditions used in the dilute acid-based process (Yang and
Wyman 2008; Chandel et al. 2011c).
The concentration of released sugars during pretreatment is directly dependent
upon the type of lignocellulosic material, composition of substrates, temperature,
time, acid concentration, solid-to-liquid ratio and the reactors employed in the
process (Lee et al. 1999; Lenihan et al. 2011; Mosier et al. 2005; Taherzadeh and
Karimi 2007; Xiang et al. 2003; Akpinar et al. 2009).
Table 2.3 shows the effect of influencing factors on sugars recovery after hemicellulosics hydrolysis from a variety of agro-residues. The cell wall composition of
the agro-residues and the operational conditions directly influence the recovery of
sugars (Shatalov and Pereira 2012). Akpinar et al. (2009) found that two different
lignocellulosic materials when subjected to similar hydrolytic conditions, showed
different levels of xylose recovery. Biomass with high lignin content released a
smaller amount of fermentable sugars due to its structural compactness. Studies
carried out at our laboratory for dilute sulfuric and oxalic acid hydrolysis of sugarcane bagasse showed efficient hydrolysis of hemicellulose (more than 80 % sugar
recovery). Figure 2.2 shows the scanning electron microscopic (SEM) analysis of
sulfuric acid and oxalic acid pretreated sugarcane bagasse.
A clear-cut distinction is visible in the cell wall compactness of sugarcane
bagasse after pretreatment compared with native sugarcane bagasse. Dilute acids
act mechanistically on hemicellulose making the overall structure quite disorganized due to the disruption of hemicellulose. Sulfuric acid is the most commonly
used acid for the pretreatment of agro-residues. Laopaiboon et al. (2010) tested
different acids for sugarcane bagasse hydrolysis and found the maximum sugar
recovery with HCl. Li et al. (2008) used double acid hydrolysis (HCl and H2SO4)
for the sugars recovery from lignocellulosic waste. Rocha et al. (2011) used a
mixture of many acids for the hydrolysis of sugarcane bagasse and reported more
than 90 % hydrolysis of the hemicellulosic fraction.

Xylose, 30

Xylose, 20

Total sugars, 57.5

D-xylose,

Sugarcane bagasse

Sugarcane bagasse

Sugarcane bagasse

Groundnut shell

Wheat straw

na not available

Dried distillers
grain (DDG)
Sugarcane bagasse

Corn cob

47.2 0.82;
4.5 0.17;
L-Arabinose, 6.2 0.29

D-Glucose,

D-Xylose,

D-glucose,

45.00 0.33;
6.40 0.21;
L-arabinose 9.00 0.12
D-glucose, 39.0 1.5 g/k of corn cob; D-Xylose
233 6.7 g/kg of corn cob
na

Xylose, 30

Wheat straw

Corn stover

Glucose, 2.39;
Xylose, 21.50; Arabinose, 5.12
Xylose, 37

Ethanol (0.41 g/g)

Ethanol (23.5 g/L)

Ethanol (0.48 g/g)

Xylitol (0.58 g/g)

Rodrigues et al.
(2011)
Canilha et al.
(2008)
Silva et al.
(2007)
Carvalho et al.
(2007)
Chandel et al.
(2007a)
Gajula et al.
(2010)
Nigam (2001)

Lactic acid (355 g/kg of corn


Guo et al.
cob)
(2010)
Aspergillus niger ATCC Citric acid (5.25 g/kg of DDG) Xie and West,
9142
(2009)
Candida langeronii RLJ Single cell protein (0.4 g/g)
Nigam (2000)
Y-019

Rhizopus oryzae GY18

P. stipitis NRRL Y7124

C. guilliermondii FTI
20037
Candida shehatae
NCIM 3501
P. stipitis NCIM 3498

Xylitol (0.59 g/g)

Candida guilliermondii
FTI 20037
C. guilliermondii
Xylitol (63 % conversion)

Xylitol (0.61 g/g)

Pichia stipitis YS-30

Table 2.3 Dilute acid hydrolysates of various for the production of various industrially significant products by microbial fermentation
Agro-residue
Sugars released (g/L)
Fermenting
Production profile of
References
hydrolysate
microorganisms
compounds (g/g or g/L)

2 Dilute Acid Hydrolysis of Agro-Residues


47

48

A. K. Chandel et al.

Fig. 2.2 Scanning electron


microscopic (SEM) analysis
of sugarcane bagasse: native
(a), dilute sulfuric acid
pretreated (b) and dilute
oxalic acid pretreated (c)

Among the factors that influence the efficiency of acid hydrolysis, temperature,
reaction time and acid concentration are the most widely investigated factors.
However, some authors investigated the influence of particle size of biomass and
solid/liquid ratio (Kapdan et al. 2011). The acid concentration is considered one of
the most important factors regarding the release of sugars. High concentrations of
acid may decompose the hemicellulosic structure, producing inhibitors and also
causing damage to the equipment used. Therefore, an appropriate acid concentration is essential for acid hydrolysis of lignocellulose at industrial scale
(Taherzadeh and Karimi 2007).
Temperature is also a crucial factor that affects directly the degradation of sugars
into inhibitors, which eventually affect microbial metabolism (Akpinar et al. 2009;
Chandel et al. 2007a). Temperature is directly connected to the energy waste of the
process (Kim et al. 2011). In general, it is observed that mild temperature led to a
significant recovery of sugars while higher temperatures caused more sugar degradation, aiding the formation of inhibitors (Yang and Wyman 2008).
According to Grio et al. (2010), sulphuric acid/hydrochloric acid concentrations for hemicellulose hydrolysis are in the range of 0.51.5 % and temperatures
between 121 and 160 C. However, there is no direct recipe or formula which can
be considered the same for all agro-residues. The pretreatment conditions will
depend on the type and species of the used vegetal biomass. Canilha et al. (2011)
found that temperature is the most important factor followed by acid concentration
and time. Neureiter et al. (2002) found that the acid concentration is the most
significant factor for hemicellulose hydrolysis. During acid pretreatment, more
severe processes cause fast sugar degradation and thus yield poor hydrolytic
efficiency (Bsch et al. 2010).

2.5 Dilute Acid Hydrolysis of Various Agro-Residues


The use of diluted acids to break down the biomass structure and recovery of the
hemicelluloses derived sugars have been studied extensively with varieties of
agricultural residues (Table 2.3). Rodrigues et al. (2010) obtained approximately

2 Dilute Acid Hydrolysis of Agro-Residues

49

74 % xylose yields from sugarcane bagasse at 130 C for 10 min using 100 mg of
sulfuric acid per gram of bagasse. Sugarcane leaves straw was submitted to dilute
acid hydrolysis under the optimized conditions (130 C, 2.9 % w/v sulfuric acid,
solid:liquid ratio 1:4, and 30 min of residence time) and produced 56.5 g/L total
reducing sugars (Mouta et al. 2011). Akpinar et al. (2009) found the optimized set
of conditions of 120 C, 30 min and 4 % acid concentration and 133 C, 27 min
and 4.9 % of acid for the hydrolysis of sunflower stalk and tobacco stalk,
respectively. Kim et al. (2011) reported the best conditions (150 C, 16.9 min and
1.16 % of acid concentration) for the maximum hemicellulose hydrolysis of barley
straw. Roberto et al. (2003) studied the parameters for diluted acid hydrolysis of
rice straw and reported the best conditions (1 % H2SO4, 27 min at 121 C) for
maximum hydrolysis.
Rahman et al. (2006) evaluated the production of xylose from oil palm empty
fruit bunch fiber using sulfuric acid. Optimum conditions (6 % H2SO4 concentration, 120 C, 15 min) produced 29.4 g/L xylose concentration. However, Zhang
et al. (2012) investigated conditions of combined dilute acid-catalyzed hydrolysis
of oil palm empty fruit bunch for the optimum production of xylose. Maximum
xylose yield (91.3 %) was obtained after hydrolysis catalyzed by 0.5 % (w/v) of
H2SO4 and 0.2 % (w/v) of H3PO4 at 160 C at a liquid to solid ratio of 20 mL/g
for 10 min. In this study, the authors concluded that combined use of H2SO4 and
H3PO4 showed a synergistic effect on improved hemicelluloses hydrolysis as
compared to H2SO4 alone. Herrera et al. (2003) evaluated the production of xylose
(16.2 g/L) from sorghum straw using HCl under the optimized set of conditions 6 % HCl, 122 C for 70 min. Mussatto and Roberto (2005) carried out
statistical optimization studies for dilute acid hydrolysis of brewers spent grain
and found the best conditions (liquid/solid ratio of 8 g/g, 100 mg H2SO4/g of dry
matter, 17 min) which yielded 92.7 % extraction of hemicellulosic sugars.

2.6 Some Aspects of Kinetics of Dilute Acid Hydrolysis


The kinetics of dilute acid hydrolysis of agro-residues mainly depends upon the
temperature of reaction, acid concentration, time, substrate concentration and
substrate composition (Mosier et al. 2005; Taherzadeh and Karimi 2007). There
are two different phases involved in dilute acid hydrolysissolid phase (agroresidues) and liquid phase (dilute acid-catalyst). Saeman (1945) initially proposed
the kinetic model for the hydrolysis of Douglas-fir wood. This model was found as
an irreversible pseudo-homogeneous first order reaction. In fact, this model was
based on the cellulose conversion into glucose followed by its conversion into
decomposition products:
k1

k2

Glucan (s) !Glucose (p) !HMF

2:1

50

K1
K2

A. K. Chandel et al.

Rate of glucan conversion into glucose


Rate of glucose decomposition into hydroxyl methyl furfural (HMF)

Both reactions can be considered as first order and irreversible. This model can
also be considered for hemicelluloses hydrolysis. McMillan (1992) reported that
hemicellulose hydrolysis at high temperature (more than 160 C) is not homogeneous and has two types of kinetic patterns, i.e. fast hydrolysis and slow
hydrolysis.
The kinetics of hemicellulose hydrolysis can be presented as follows (Lee et al.
1999):

where
H1
Kinetics of hemicelluloses hydrolysis (easy to hydrolyse)
H2
Kinetics of hemicelluloses hydrolysis (difficult to hydrolyse)
Grohman et al. (1986) proposed that the dilute acid hydrolysis of hemicellulose
is a pseudo-homogenous first order reaction consisting of a fast hydrolyzing
reaction and a slow hydrolyzing reaction. Lenihan et al. (2011) described the
hemicellulose hydrolysis as follows:
k1

k2

Hemicellulose (s) !soluble sugars (p) !decomposition products


Monomers (xylose or other sugars) concentration (M) is a function of
time (t) which can be represented as:
M k1  P0 =k2  k1 ek 1 t  ek 2 t M 0 ek 2 t

2:2

where
M
Monomer concentration (g/L)
P
Polymer concentration (g/L)
MO
Initial monomer concentration (g/L)
Consider that initial monomer concentration (MO) is equal to zero, then
Eq. (2.2) can be represented as (Lenihan et al. 2011):
M k1 :P0 =k2  k1 ek 1 t  ek 2 t

2:3

As described before, there are two fractions in hemicellulose polymer, i.e. fast
hydrolyzing and slow hydrolyzing. The ratio between both the fractions is a. This
equation can be further simplified as (Lenihan et al. 2011):

2 Dilute Acid Hydrolysis of Agro-Residues

M ak1 :P0 =k2  k1 ek 1 t  ek 2 t

51

2:4

If hemicelluloses hydrolysis is 100 % fast hydrolyzing then a 1 g=g:

2.7 Process Configurations Considering the Reactors used


for Dilute Acid Hydrolysis
Dilute acid hydrolysis is probably one of the most common and largely explored
methods to hydrolyse the hemicellulosic fraction of agro-residues or other lignocellulosic materials. Batch hydrolysis is the simplified process where substrate and
dilute acid are mixed first followed by the reaction at high temperature for a certain
period of time and recovery of the liquid fraction consisting of hemicellulosicderived sugars in addition to cell wall-derived inhibitors. The acid-pretreated agroresidues are enzymatically digested to depolymerise cellulose into glucose.
Among all the available technologies, dilute acid hydrolysis followed by
enzymatic hydrolysis by less expensive and more efficient cellulases has been
found more promising towards the potential economics and environmental impact
(Taherzadeh and Karimi 2007; Chandel et al. 2007b). Dilute acid hydrolysis was
first demonstrated by Faith (1945) treating wood chips with dilute sulfuric acid
(0.5 %) for 45 min at 1112 bar pressure. Since then, a lot of developments have
been seen aiming towards the development of a dilute acid hydrolysis process with
less acid load, less reaction time and high temperature.
Batch processes of dilute acid hydrolysis generally show more than 80 %
recovery of hemicellulose (xylose-rich hydrolysate containing arabinose, mannose,
glucose and galactose) in addition to cell wall-derived inhibitors (furfurals,
5-hydroxy methyl furfural, weak organic acids, lignin derived phenolics and
others). Batch hydrolysis can be carried out in a variety of vessels (Erlenmeyer
flasks to stainless cylindrical steel vessels, Parr reactor, stirred tank reactor,
rotating drum reactor, etc.). Lignocellulosic material and dilute acid are added in
Erlenmeyer flasks or cylindrical vessels made of stainless steel which are kept in
autoclave, Parr reactor or oil bath reactor for reaction at higher temperatures. The
required temperature in a Parr reactor, stirred tank reactor and drum reactors is
approached by providing heat or cooling water from an outside source through the
jacket. Figure 2.3 shows the examples of vessels/reactors used for dilute acid
hydrolysis at the Engineering School of Lorena, University of Sao Paulo (USP),
Lorena, So Paulo, Brazil. Dilute acid hydrolysis is carried out in two stages.

2.7.1 First-Stage Dilute Acid Hydrolysis


The lignocellulosic material is first placed in contact with dilute sulfuric acid
(0.75 %) and heated to approximately 50 C, then transferred to the first-stage acid

52

A. K. Chandel et al.

Fig. 2.3 Systems explored for dilute acid hydrolysis of various agro-residues at Engineering
School of Lorena (EEL), University of Sao Paulo, Lorena. a Large reactor of capacity 1,000 L.
b Medium size rotator reactor. c Autoclave equipped for acid hydrolysis of biomass. d Parr
reactor. e Oil bath reactor with stainless steel made hydrolytic vessels. f Medium size static
reactor

impregnator where the temperature is raised to 190 C. Approximately, 80 % of


the hemicellulose and 29 % of cellulose are hydrolyzed in the first reactor. The
hydrolysate is further incubated at a lower temperature for a residence time of 2 h
to hydrolyse most of the oligosaccharides into monosaccharides followed by the
separation of solid and liquid fractions (Chandel et al. 2007b). The solid material is
then again washed with plenty of water to maximize sugar recovery. The separated
solid material is sent to the second-stage acid hydrolysis reactor. Figure 2.4 shows
the configuration outline of batch processes for acid hydrolysis of lignocellulosic
materials.

2 Dilute Acid Hydrolysis of Agro-Residues

53

Fig. 2.4 Modified reactors configured for batch and continuous hydrolysis of agro-residues
(Batch reactor, continuous reactors: counter-current, percolation reactor, plug-flow and shrinkingbed reactor)

2.7.2 Two-Stage Dilute Acid Hydrolysis


In the two-stage dilute acid hydrolysis process, first, biomass is treated with dilute
acid at relatively mild conditions during which the hemicelluose fraction is
hydrolyzed, and the second stage is normally carried out at a higher temperature
for depolymerisation of cellulose into glucose (Nguyen et al. 2000). The liquid
phase, containing the monomeric sugars is removed between the treatments,
thereby avoiding degradation of monosaccharides formed. Sanchez et al. (2004)
carried out the two-stage dilute acid hydrolysis using Bolivian straw material, Paja
brava. In the first stage, P. brava was pretreated with steam followed by dilute
sulfuric acid (0.5 or 1.0 % by wt.) hydrolysis at temperatures between 170 and
230 C for a residence time between 3 and 10 min. The highest yield of hemicellulose-derived sugars was found at a temperature of 190 C, and a reaction time
of 510 min, whereas in second stage hydrolysis considerably higher temperature
(230 C) was found for hydrolysis of the remaining fraction of cellulose.
The two-stage dilute acid hydrolysis process is generally preferred over the
first-stage dilute acid hydrolysis process due to less energy requirements,

54

A. K. Chandel et al.

minimization of sugars degradation and less derivation of inhibitors (Nguyen et al.


2000). Batch hydrolysis processes are most commonly employed for the hydrolysis of lignocellulosic materials. However, continuous processes for dilute acid
hydrolysis have also been employed.

2.7.3 Continuous (Percolation Reactor, Plug-Flow Reactor,


Counter-Current Reactor, Shrinking-Bed Reactor)
Figure 2.4 describes the configuration outline of the continuous dilute acid
hydrolysis process employed for the acid hydrolysis of agro-residues.

2.7.3.1 Plug-Flow Reactor


Figure 2.4 shows the conceptual diagram of Plug flow reactor (PFR). In a PFR, it
is quite difficult to control short residence time of biomass pretreatment (range of
few seconds). Low concentration of acids is required in PFR in conjunction with
high temperature (200240 8C). Heat transfer limitations are also apparent due to
uneven reaction within biomass that eventually reduces the overall sugar yield. In
general, 5070 % yield of sugars are obtained in PFRs (Lee et al. 1999; Taherzadeh and Karimi 2007).

2.7.3.2 Percolation Reactor (Packed-Bed Flow Through Reactor)


Percolation reactors are easy to use for dilute acid hydrolysis of lignocellulosic
biomass due to immovable biomass and liquid fraction. In the percolation reactor,
sugars can be obtained as they are formed and thus minimize the chances of sugar
degradation consequently releasing a high amount of sugars (Lee et al. 1999).
Figure 2.4 shows the conceptual diagram of a percolation reactor. There are many
benefits to using a percolation reactor. High lignocellulosic biomass-to-liquid ratio
can be used in a percolation reactor. Hydrolysate is easily removed from the solid
fraction. An optimized feeding of solid and liquid is an important parameter to get
the high sugars yield in the reactor. Slow feeding of lignocellulosic material will
cause high sugar degradation while very fast feeding will leave the substrate
untreated. In both circumstances, low sugar yield is obtained. On the basis of
kinetics of hydrolysis reaction, a percolation reactor can be divided into two types:
(1) a step change of temperature and optimum temperature difference, and (2) a
two-stage reverse-flow percolation reactor. The former percolation strategy
constituted two different basic characteristics (fast-hydrolysing and slow
hydrolyzing reactions). Temperature change during the process, particularly a step
change from uniform low to uniform high, showed the improved results (Lee et al.

2 Dilute Acid Hydrolysis of Agro-Residues

55

1999). In a two-stage reverse flow percolation reactor, the biomass is first pretreated at low temperature followed by high temperature reaction. The striking
difference between a step-change and two-stage reverse flow percolation reactor is
stream from high temperature is again exposed to fresh biomass at low
temperature. The treated solid residue in this reactor is then treated with fresh acid
at high temperature. This process is regularly repeated (Lee et al. 1999; Taherzadeh and Karimi 2007).
2.7.3.3 Counter-Current Reactor
These reactors are specialized moving bed reactors in which the direction of solid
and liquid are reversed. Figure 2.4 shows the conceptual diagram of a countercurrent reactor. A high concentration of sugars is obtained in counter-current
reactors. The major part of sugars is formed near the liquid outlet point. The
stream moves relatively short distances before it is washed out of the reactor thus
reducing the time period for the sugar degradation, eventually increasing the high
sugars yield (Lee et al. 1999; Taherzadeh and Karimi 2007). These reactors offer
great advantages over plug flow or percolation reactors.
2.7.3.4 Shrinking Bed Counter-Current Reactor
Continuous counter current reactors have the property of bed shrinking causing
improvements in sugars recovery with minimized sugar degradation. The shrinking bed causes the change of solid velocity within the reactor which improves the
hydrolysis efficiency (Lee et al. 1999). Figure 2.4 shows the conceptual diagram of
a shrinking bed counter-current reactor.

2.8 Economics and Environmental Aspects


The major parameters which influence the cost of dilute acid hydrolysis of agroresidues are the cost of raw material, amount of catalytic agent (acid) and utility
expenses (steam, cooling water, electricity and maintenance of reactors) (Yang and
Wyman 2008). The cost impact of these parameters directly influences the sugar
recovery, processing time and generation of inhibitors. An ideal dilute acid
hydrolysed process is one which has minimum operational and functional cost
while largely influencing sugars recovery with the least amount of inhibitors
generation (Yang and Wyman 2008). Removal of inhibitors from acid hydrolysates prior to fermentation adds the extra cost in biomass conversion. A generalized procedural break-up of expenses in ethanol production from lignocellulosic
feedstock(s) shows that the cost of raw material (almost 34 %) is the main
important factor to be considered, followed by total pretreatment cost (17.5 %),
boiler energy (8.5 %) and utilities and storage (5 %) (Viikari 2004). Among the

56

A. K. Chandel et al.

LCF, agro-residues such as sunflower stalk, Brassica compestris stalks, cotton


stalks, sugarcane leaves, groundnut shell, etc., which have minimum food/feed
value and commercial applications would be of paramount importance.
Dilute acid hydrolysis of agro-residues in batch processes usually done using
low concentration of acids, high temperature, and different time variations eventually release moderate amounts of sugars recovery (8085 %) with considerable
amount of cell wall derived inhibitors (Canilha et al. 2011). Dilute acid hydrolysis
using modified continuous reactors (plug flow, percolation, counter-current and
shrinking-bed) generally occur at high temperature (200240 C) for a short time
(less than 1 min) using low acid concentration (Lee et al. 1999). Counter-current
operations could be more economic in terms of yielding high amounts of sugars in
short times with less operational cost (Lee et al. 1999). National Renewable
Energy Laboratory (NREL)-based process engineering studies have developed a
fully-integrated and mature material balance and financial modules (ASPEN
PLUS) process simulation which can provide the net economic analysis of dilute
acid hydrolysis of various agro-residues (Mosier et al. 2005).
With regards to net impact of dilute acid hydrolysis-based protocols on the
environment, it can be stated that these processes are not very environmentally
friendly (Taherzadeh and Karimi 2008). However, a much diluted concentration of
acids is used in dilute acid hydrolysis of agro-residues. In addition to acid load, a
high temperature range also poses a negative effect and an overall impact on the
environment. Hemicellulase enzyme-based catalysed processes certainly have
advantages over acid catalysed processes (Grio et al. 2010). However, looking at
the high sugars recovery in short time periods, dilute acid hydrolysis is still
considered as a favorite compared to enzyme-based processes for hemicellulose
break-down. Considering less acid load at high temperature is a preferred method
since it causes less environmental pollution compared with strong acid hydrolysis.
Another significant advantage using dilute acid hydrolysis is that generation of a
low amount of inhibitors eventually requires milder detoxification methods to
eliminate the inhibitors.

2.9 Conclusion and Future Recommendations


Agro-residues constitute the important part of total biomass available on earth for
their readily available application in bioconversion systems. However, pretreatment of agro-residues with dilute acid hydrolysis is an important step for their
fullest utilization. Dilute acids catalyze the hemicellulose degradation into simpler
constituents and thus increase the amenability of cellulolytic enzymes towards the
hydrolysis of the cellulosic fraction into fermentable feedstock. During hemicellulose hydrolysis by dilute acid catalyzed processes, a number of inhibitors are
also generated which hamper the fermentation reaction for the production of
important metabolites by microorganisms. In the last 30 years, significant work
has been carried out in order to establish the successful and reproducible

2 Dilute Acid Hydrolysis of Agro-Residues

57

technological protocol for hemicellulose depolymerisation with fewer number of


inhibitors. Parameters involved in dilute acid hydrolysis of agro-residues viz. acid
load, substrate to liquid ratio, residence time and temperature play the decisive role
in obtaining the maximum hydrolysis efficiency. Consideration of these parameters
also depends upon the selection of raw material. Batch reactors have been used
more often for agro-residues hydrolysis. However, various modifications in reactors have also been adopted in order to maximize hemicellulose hydrolysis within
short time periods. Reactor modifications such as percolation, plug-flow, countercurrent and shrinking bed have been used for acid hydrolysis of agro-residues.
Counter-current reactors have shown improved results in some studies carried out
at the National Renewable Energy Laboratory (NREL), Colorado, USA. Better
understanding of kinetic models for their implication in these reactor modifications
may further improve the hemicellulose hydrolysis. Economics and environmental
impact are two important considerations for the selection of dilute acid hydrolysisbased pretreatment technology. In future, technologies based on robust optimization tools for dilute acid hydrolysis, finding the ideal acid or mixed dilute acids
considering the basic parameters and suitable reactors would be the ultimate
choice. Application of nano-particles-based membrane systems and their implication in hemicellulose hydrolysis may also provide better results in short times
with fewer by-products.
Acknowledgments We are grateful to the BIOEN/FAPESP, CNPq and CAPES, Brazil for
financial assistance.

References
Akpinar O, Erdogan K, Bostanci S (2009) Production of xylooligosaccharides by controlled acid
hydrolysis of lignocellulosic materials. Carbohyd Res 344:660666
Anupama A, Ravindra P (2000) Value-added food: single cell protein. Biotechnol Adv 18:459479
Baek S-C, Kwon Y-J (2007) Optimization of the pretreatment of rice straw hemicellulosic
hydrolyzates for microbial production of xylitol. Biotechnol Bioproc Eng 12:404419
Bsch P, Wallberg O, Joelsson E, Galbe M, Zacchi G (2010) Impact of dual temperature profile
in dilute acid hydrolysis of spruce for ethanol production. Biotechnol Biofuels 3:15
Boussarsar H, Rog B, Mathlouthi M (2009) Optimization of sugarcane bagasse conversion by
hydrothermal treatment for the recovery of xylose. Biores Technol 100:65376542
Branco RF, Santos JC, Sarrouh BF, Rivaldi JD, Pessoa Jr A, Silva SS (2008) Profiles of xylose
redutase, xylitol dehydrogenase and xylitol production under different oxygen transfer
volumetric coefficient values. J Chem Technol Biotechnol 84:324330
Brunow G, Lundquist K, Gellerstedt G (1999) Lignin. In: Sjstrm E, Aln R (eds) Analytical
methods in wood chemistry, pulping, and paper making. Springer, Berlin, pp 77124
Bura R, Chandra R, Saddler J (2009) Influence of xylan on the enzymatic hydrolysis of steampretreated corn stover and hybrid poplar. Biotechnol Prog 25:315322
Canilha L, Carvalho W, Silva JBA (2006) Xylitol bioproduction from wheat straw: hemicellulose
hydrolysis and hydrolyzate fermentation. J Sci Food Agric 86:13711376
Canilha L, Carvalho W, Felipe MGA, Silva JBA (2008) Xylitol production from wheat straw
hemicellulosic hydrolysate: hydrolysate detoxification and carbon source used for inoculum
preparation. Braz J Microbiol 39:333336

58

A. K. Chandel et al.

Canilha L, Santos VTO, Rocha GJM, Almeida e Silva JB, Giulietti M, Silva SS, Felipe MGA,
Ferraz A, Milagres AMF, Carvalho W (2011) A study on the pretreatment of sugarcane
bagasse sample with dilute sulfuric acid. J Ind Microbiol Biotechnol 38:14671475
Cao G, Ren N, Wang A, Lee DJ, Guo W, Liu B, Feng Y, Zhao Q (2009) Acid hydrolysis of corn
stover for biohydrogen production using Thermoanaerobacterium thermosaccharolyticum
W16. Int J Hyd Ener 34:71827188
Carvalheiro F, Duarte LC, Medeiros R, Grio FM (2004) Optimization of brewerys spent grain
dilute-acid hydrolysis for the production of pentose-rich culture media. Appl Biochem
Biotechnol 113116:10591072
Carvalheiro F, Duarte LC, Grio FM (2008) Hemicellulose biorefineries: a review on biomass
pretreatments. J Sci Ind Res 67:849864
Carvalho W, Canilha L, Silva SS (2007) Semi-continuous xylitol bioproduction in sugarcane
bagasse hydrolysate: effect of nutritional supplementation. Rev Bras Cienc Farm 43:4753
Chandel AK, Kapoor RK, Singh AK, Kuhad RC (2007a) Detoxification of sugarcane bagasse
hydrolysate improves ethanol production by Candida shehatae NCIM 3501. Biores Technol
98:19471950
Chandel AK, Chan EC, Rudravaram R, Narasu ML, Rao LV, Ravindra P (2007b) Economics and
environmental impact of bioethanol production technologies: an appraisal. Biotechnol Mol
Biol Rev 2:1432
Chandel AK, Narasu ML, Rudravaram R, Ravindra P, Narasu ML, Rao LV (2009) Bioconversion
of de-oiled rice bran (DORB) hemicellulosic hydrolysate into ethanol by Pichia stipitis
NCIM3499 under optimized conditions. Int J Food Eng 2:112
Chandel AK, Singh OV, Chandrasekhar G, Rao LV, Narasu ML (2010a) Key-drivers influencing
the commercialization of ethanol based biorefineries. J Comm Biotechnol 16:239257
Chandel AK, Singh OV, Rao LV (2010b) Biotechnological applications of hemicellulosic
derived sugars: state-of-the-art. In: Singh OV, Harvey SP (eds) Sustainable biotechnology:
renewable resources and new perspectives. Springer, Dordrecht, pp 6381
Chandel AK, Silva SS, Carvalho W, Singh OV (2011a) Sugarcane bagasse and leaves:
foreseeable biomass of biofuel and bio-products. J Chem Technol Biotechnol 87:1120
Chandel AK, Silva SS, Singh OV (2011b) Detoxification of lignocellulosic hydrolysates for
improved bioconversion of bioethanol. In: Bernardes MAS (ed) Biofuel production-recent
developments and prospects. InTech, Rijeka
Chandel AK, Chandrasekhar G, Silva MB, Silva SS (2011b) The realm of cellulases in
biorefinery development. Crit Rev Biotechnol. doi:10.3109/07388551.2011.595385
Cheng KK, Zhang J-A, Ling HZ, Ping W-X, Huang W, Ge J-P, Xu J-M (2009) Optimization of
pH and acetic acid concentration for bioconversion of hemicellulose from corncobs to xylitol
by Candida tropicalis. Biochem Eng J 43:203207
Cruz JM, Domnguez H, Paraj JC (2000) Preparation of fermentation media from agricultural
wastes and their bioconversion to xylitol. Food Biotechnol 14:7997
Dehnavi GZ (2009) Fractionation of the main components of barley spent grains from a
microbrewery. University of Bors, Sweden, Dissertation
Dogaris I, Vakontios G, Kalogeris E, Mamma D, Kekos D (2009) Induction of cellulases and
hemicellulases from Neurospora crassa under solid-state cultivation for bioconversion of
sorghum bagasse into ethanol. Ind Crops Prod 29:404411
Doherty WOS, Mousavioun P, Fellows CM (2011) Value-adding to cellulosic ethanol: lignin
polymers. Ind Crops Prod 33:259276
Duarte LC, Carvalheiro F, Lopes S (2008) Yeast biomass production in brewerys spent grains
hemicellulosic hydrolyzate. Appl Biochem Biotechnol 148:119129
Ek M, Gellerstedt G, Henriksson G (eds) (2009) Pulp and paper chemistry and technology, wood
chemistry and wood biotechnology. De Gruyter, Berlin, pp 1320
Faith WL (1945) Development of the Scholler process in the United States. Ind Eng Chem 37:911
Felipe MGA, Vitolo M, Mancilha IM, Silva SS (1997) Environmental parameters affecting
xylitol production from sugarcane bagasse hemicellulosic hydrolisate by Candida
guilliermondii. J Ind Microbiol 18:251254

2 Dilute Acid Hydrolysis of Agro-Residues

59

Fengel D, Wegener G (1984) Woodchemistry, ultrastructure, reactions. Walterde Gruyter, Berlin


Gajula CS, Konakalla R, Chandel AK, Kumari TDS, Rudravaram R, Mangamoori ML (2010)
Bioconversion of groundnut shell hemicellulose hydrolysate into fuel ethanol production by
Pichia stipitis NCIM 3498. Technol Spec 4:3136
Grio FM, Fonseca C, Carvalheiro F, Duarte LC, Marques S, Bogel-lukasik R (2010)
Hemicelluloses for fuel ethanol: a review. Biores Technol 101:47754800
Grohmann K, Torget RW, Himmel M (1986) Dilute acid pretreatment of biomass at high solids
concentrations. Biotechnol Bioeng Symp 17:135151
Guo Y, Yan Q, Jiang Z, Teng C, Wang X (2010) Efficient production of lactic acid from sucrose
and corncob hydrolysate by a newly isolated Rhizopus oryzae GY18. J Ind Microbiol
Biotechnol 37:11371143
Herrera A, Tllez-Luis S J, Ramrez JA, Vzquez M (2003) Production of xylose from Sorghum
straw using hydrochloric acid. J Cereal Sci 37:267274
Howard RL, Abotsi E, Van Rensburg ELJ, Howard S (2003) Lignocellulose biotechnology:
Issues of bioconversion and enzyme production. Afr J Biotechnol 2:602609
Kapdan IK, Kargi F, Oztekin R (2011) Effects of operating parameters on acid hydrolysis of
ground wheat starch: Maximization of the sugar yield by statistical experiment design. Starch
- Strke 63:311318
Kim SB, Lee JH, Oh KK, Lee SJ, Lee JY, Kim JS, Kim SW (2011) Diluted acid pretreatment of
barley straw and its saccharification and fermentation. Biotechnol Bioproc Eng 16:725732
Kirimura K, Watanabe T, Sunagawa T (1999) Citric acid production from xylan and xylan
hudrolysate by semi-solid culture of Arpergilus niger. Biosci Biotechnol Biochem 63:226228
Laopaiboon P, Thani A, Leelavatcharamas V, Laopaiboon (2010) Acid hydrolysis of sugarcane
bagasse for lactic acid production. Biores Technol 101:10361043
Lee YY, Iyer P, Torget RW (1999) Dilute-acid hydrolysis of lignocellulosic biomass. Adv
Biochem Eng Biotechnol 65:93115
Lenihan P, Orozco A, ONeill E, Ahmad MNM, Rooney DW, Mangwandi C, Walker GM (2011)
Kinetic modelling of dilute acid hydrolysis of lignocellulosic biomass. In: Bernardes MAS
(ed) Biofuel production-recent developments and prospects. InTech, Rijeka
Li WZ, Xu J, Yan YJ, Zhu XF, Chen MQ, Tan ZC (2008) Studies of monosaccharide production
through lignocellulosic waste hydrolysis using double acids. Energy Fuels 22(3):20152021
Mantanis G, Nakos P, Berns J, Rigal L (2000) Turning agricultural straw residues into valueadded composite products: a new environmentally friendly technology. Proceedings of the 5th
international conference on environmental pollution, pp 840848, Aristotelian University,
Thessaloniki, Greece
Martn C, Puls J, Saake B, Schreiber A (2011) Effect of glycerol preatreatment on component
recovery and enzymatic hydrolysis of sugarcane bagasse. Cellul Chem Technol 45:487494
Mcmillan JD (1992) NREL Report TP-4214978. Golden, CO, USA
Megawati Sediawan WB, Sulistyo H, Hidayat M (2011) Kinetics of sequential reaction of
hydrolysis and sugar degradation of rice husk in ethanol production: Effect of catalyst
concentration. Biores Technol 102:20622067
Milessi TSS, Chandel AK, Branco RF, Silva SS (2011) Effect of dissolved oxygen and inoculum
concentration on xylose reductase production from Candida guilliermondii using sugarcane
bagasse hemicellulosic hydrolysate. Food Nut Sci 2:235240
Mosier N, Wyman C, Dale B, Elander R, Lee YY, Holtzapple M, Ladisch M (2005) Features of
promising technologies for pretreatment of lignocellulosic biomass. Biores Technol 96:673686
Mouta RO, Chandel AK, Rodrigues RCLB, Silva MB, Rocha GJM, Silva SS (2011) Statistical
optimization of sugarcane leaves hydrolysis into simple sugars by dilute sulfuric acid
catalyzed process. Sugar Tech. doi:10.1007/s12355-011-0116-y
Mussatto SI, Roberto IC (2005) Acid hydrolysis and fermentation of brewers spent grain to
produce xylitol. J Sci Food Agr 85:24532460
Mussatto SI, Teixeira JA (2010) Lignocellulose as raw material in fermentation processes. In:
Mndez-Vilas A (ed) Current research, technology and education topics in applied microbiology
and microbial biotechnology, vol 2. Formatex Research Center, Badajoz, Spain, pp 897907

60

A. K. Chandel et al.

Mussatto SI, Fernandes M, Roberto IC (2007) Lignin recovery from brewers spent grain black
liquor. Carbohyd Polym 70:218223
Mussatto SI, Carneiro LM, Silva JPA, Roberto IC, Teixeira JA (2011) A study on chemical
constituents and sugars extraction from spent coffee grounds. Carbohyd Polym 83:368374
Neureiter M, Danner H, Thomasser C, Saidi B, Braun R (2002) Dilute-acid hydrolysis of
sugarcane bagasse at varying conditions. Appl Biochem Biotechnol 98100:4958
Nguyen Q, Tucker M, Keller F, Eddy F (2000) Two-stage dilute-acid pretreatment of softwoods.
Appl Biochem Biotechnol 84:561576
Nigam JN (2000) Cultivation of Candida langeronii in sugar cane bagasse hemicellulosic
hydrolyzate for the production of single cell protein. World J Microbiol Biotechnol 16:367372
Nigam JN (2001) Ethanol production from wheat straw hemicelluloses hydrolysate by Pichia
stipitis. J Biotechnol 87:1727
Ou MS, Ingram LO, Shanmugam KT (2011) L: (+)-Lactic acid production from non-food
carbohydrates by thermotolerant Bacillus coagulans. J Ind Microbiol Biotechnol 38:599605
Rabelo SC, Carrere H, Maciel filho R, Costa AC (2011) Production of bioethanol, methane and
heat from sugarcane bagasse in a biorefinery concept. Biores Technol 102:78877895
Rahman SHA, Choudhury JP, Ahmad AL (2006) Production of xylose from oil palm empty fruit
bunch fiber using sulfuric acid. Biochem Eng J 30:97103
Roberto IC, Mussatto SI, Rodrigues RCLB (2003) Dilute-acid hydrolysis for optimization of
xylose recovery from rice straw in a semi-pilot reactor. Ind Crops Prod 17:171176
Rocha GJM, Martin M, Soares IB, Maior AMS, Baudel HM, Abreus CAM (2011) Dilute mixedacid pretreatment of sugarcane bagasse for ethanol production. Biomass Bioener 35:663670
Rocha GJM, Gonalves AR, Oliveira BR, Olivares EG, Rossell CEV (2012) Steam explosion
pretreatment reproduction and alkaline delignification reactions performed on a pilot scale
with sugarcane bagasse for bioethanol production. Ind Crops Prod 35:274279
Rodrigues RCLB, RochaGJM, Rodrigues Jr D, Filho HJI, Felipe MGA, Pessoa Jr A (2010) Scaleup of diluted sulfuric acid hydrolysis for producing sugarcane bagasse hemicellulosic
hydrolysate (SBHH). Biores Technol 101:12471253
Rodrigues RC, Kenealy WR, Jeffries TW (2011) Xylitol production from DEO hydrolysate of
corn stover by Pichia stipitis YS-30. J Ind Microbiol Biotechnol 38:16491655
Rowell RM, Pettersen R, Han JS, Rowell JS, Tshabalala MA (2005) Cell wall chemistry. In:
Rowell RM (ed) Handbook of wood chemistry and wood composites. CRC Press, Boca
Raton, pp 3574
Ruiz E, Cara C, Manzanares P, Ballesteros M, Castro E (2008) Evaluation of steam explosion pretreatment for enzymatic hydrolysis of sunflower stalks. Enzyme Microb Technol 42:160166
Saeman JF (1945) Kinetics of wood saccharification. Ind Eng Chem 37:4352
Saha BC (2003) Hemicellulose bioconversion. J Ind Microbiol Biotechnol 30:279291
Sanchez G, Pilcher L, Roslander C, Modig T, Galbe M, Liden G (2004) Dilute-acid hydrolysis for
fermentation of the Bolivian straw material Paja brava. Biores Technol 93:249256
Seplveda-Huerta E, Tellez-Luis SJ, Bocanegra-Garca V, Ramrez JA, Vzquez M (2006)
Production of detoxified sorghum straw hydrolysates for fermentative purposes. J Sci Food
Agr 86:25792586
Shatalov AA, Pereira H (2012) Xylose production from giant reed (Arundo donax L.): modeling
and optimization of dilute acid hydrolysis. Carbohyd Polym 87:210217
Silva SS, Musstto SI, Santos JC, Santos DT, Polizel J (2007) Cell immobilization and xylitol
production using sugarcane bagasse as raw material. Appl Biocehm Biotechnol 141:215227
Silva AS, Inoue H, Endo T, Yano S, Bon EPS (2010a) Milling pretreatment of sugarcane bagasse
and straw for enzymatic hydrolysis and ethanol fermentation. Biores Technol 101:74027409
Silva SS, Mussatto SI, Santos JC, Santos DT, Polizel J (2010b) Cell immobilization and xylitol
production using sugarcane bagasse as raw material. Appl Biochem Biotechnol 141:215228
Silva VFN, Arruda PV, Felipe MGA, Gonalves AR, Rocha GJM (2010c) Fermentation of
cellulosic hydrolysates obtained by enzymatic saccharification of sugarcane bagasse
pretreated by hydrothermal processing. J Ind Microbiol Biotechnol 38:809817

2 Dilute Acid Hydrolysis of Agro-Residues

61

Sjstrm E (1993) Wood polysaccharides. In: Sjstrm E (ed) Wood chemistry: Fundamentals
and applications, 2nd edn. Academic Press, New York, pp 5470
Taherzadeh MJ, Karimi K (2007) Acid based hydrolysis process for bioethanol production from
lignocellulosic materials: a review. BioRes 2:472499
Taherzadeh MJ, Karimi K (2008) Pretreatment of lignocellulosic wastes to improve ethanol and
biogas production: a review. Int J Mol Sci 9:16211651
Tamanini C, Oliveira AS, Felipe MGA, Canettieri EV, Cndido EJ, Hauly MCO (2004)
Avaliao da casca de aveia para a produo biotecnolgica de xilitol. Acta Sci Technol
26:117125
Tllez-Luis SJ, Ramrez JA, Vzquez M (2002) Mathematical modelling of hemicellulosic sugar
production from Sorghum straw. J Food Eng 52:285291
Viikari L (2004) Overcoming technical barriers in bioethanol production from lignocellulosics.
European-China workshop on liquid biofuels; 45 Novemb, Beijing
Xiang Q, Kim JS, Lee YY (2003) A comprehensive kinetic model for dilute-acid hydrolysis of
cellulose. Appl Biochem Biotechnol 105108:337352
Xie G, West T (2009) Citric acid production by Aspergillus niger ATCC 9142 from a treated ethanol
fermentation co-product using solid-state fermentation. Lett Appl Microbiol 48:639644
Yang B, Wyman CE (2008) Pretreatment: the key to unlocking low cost cellulosic ethanol.
Biofuels Biopr Bioref 2:2640
Zhang D, Ong YL, Li Z, Wua JC (2012) Optimization of dilute acid-catalyzed hydrolysis of oil
palm empty fruit bunch for high yield production of xylose. Chem Eng J 181182:636642
Zhao X, Song Y, Liu D (2011) Enzymatic hydrolysis and simultaneous saccharification and
fermentation of alkali/peracetic acid-pretreated sugarcane bagasse for ethanol and 2, 3
butanediol production. Enzyme Microb Technol 49:413419

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